KR20210056244A - Phenalkamine epoxy curing agents from methylene bridged poly(cyclohexyl-aromatic) amines and epoxy resin compositions containing the same - Google Patents

Abstract

The present invention relates to novel structural classes of phenalkamines, a phenalkamine curing agent composition, a method for preparing such phenalkamines, and a method for preparing the composition. The phenalkamine curing agent composition of the present invention can be prepared by making cardanol react with a mixture of an aldehyde compound and a methylene crosslinked poly(cycloaliphatic-aromatic)amine. The curing agent composition may be used to cure, harden, and/or crosslink epoxy resins.

Description

Phenalkamine epoxy curing agent from methylene cross-linked poly(cyclohexyl-aromatic) amine and epoxy resin composition containing it {PHENALKAMINE EPOXY CURING AGENTS FROM METHYLENE BRIDGED POLY(CYCLOHEXYL-AROMATIC) AMINES AND EPOXY RESIN COMPOSITIONS CONTAINING THE SAME}

The Mannich reaction is based on the reaction of aldehydes such as formaldehyde with phenolic compounds and amines. Various types of phenolic compounds, amines and aldehydes are used in this reaction. Mannich base products are particularly suitable for curing epoxy resins.

The phenalkamine curing agent is a series of Mannich bases obtained by reacting cardanol, a phenolic extract of cashew nut shell liquid, an aldehyde compound such as formaldehyde, and an amine. Generally, it is prepared from the reaction of 1 molar equivalent of cardanol with 1 to 2 molar equivalents of aliphatic polyethylene polyamine and 1 to 2 molar equivalents of formaldehyde at 80-100°C. Aromatic polyamines are also suitable for this reaction.

Phenalkamine NC 541 and NC 540 commercially available from Cardolite Inc. and Sunmide CX105 available from Evonik Corp. are ethylenediamine and diethylene as amine sources as amine sources. Triamine is used. Sunmid 1151 phenalkamine, available from Evonik Corporation, uses m-xylenediamine as an amine source.

Phenalkamine is an excellent epoxy resin hardener for room temperature or low temperature cure applications. In addition, it provides good chemical resistance, excellent water resistance, good compatibility with epoxy resins, low toxicity and good flexibility. Consequently, it is used in marine, industrial maintenance and civil engineering applications.

GB Patent No. 1,529,740 describes phenalkamine as a mixture of poly(aminoalkylene) substituted phenols (structure below) prepared from cardanol and polyethylene polyamines and formaldehyde. In general, easy control of the molecular weight distribution of these products is not possible and therefore it is mostly a viscous liquid.

R = hydrocarbyl substituent having 15 carbon atoms, x = 1-5, n = 1-3, R'= H.

U.S. Patent No. 6,262,148 B1 describes a composition of phenalkamine having an aromatic or alicyclic ring. These compositions were prepared from cardanol and aldehydes and alicyclic or aromatic polyamines. International Application Publication No. WO 2009/080209 A1 describes the preparation of an epoxy curing agent comprising phenalkamine blended with a polyamine salt. This curing agent was used to improve the curing speed of the epoxy resin.

Brief summary of the invention

The present invention relates to a phenalkamine obtained using a mixture of methylene crosslinked poly(cycloaliphatic-aromatic) amines (sometimes referred to as "MPCA") as amine source. Accordingly, the present disclosure discloses a novel structural family of phenalkamine, a curing agent composition, a method of preparing such phenalkamine, and a method of preparing such a composition. Such curing agent compositions can be used to cure, harden and/or crosslink the epoxy resin. Additionally, these phenalkamine curing agents of the present invention can provide dry curing of epoxy coatings after <8 h at ambient temperature (23° C.) or after <16 h at 5° C., and have improved low temperature surface appearance and improved chemical resistance. It provides improved coating performance as demonstrated by. Due to the combination of these properties, MPCA based phenalkamine can additionally be used as a curing agent for cold tank linings that require improved chemical resistance for the transport and storage of chemicals in the oil and gas field.

The MPCA-based phenalkamine of the present invention has the advantage of providing a faster amine-epoxy reaction rate compared to the state-of-the-art phenalkamine. This unique property offers the advantage of a lower tendency to carbamate and shorter coating drying times compared to traditional phenalkamine products derived from alkylene amines such as ethylenediamine. In addition, the coating composition based on the MPCA phenalkamine curing agent of the present invention is very good for a variety of chemical reagents including alcohol (ethanol, methanol), xylene, ketone (methyl isobutyl ketone), caustic soda and sulfuric acid. It exhibits resistance and in this respect is superior to coatings made from phenalkamine derived from ethylenediamine.

In the preparation of MPCA mixtures, the condensation product of formaldehyde and aniline or toluidine containing significant amounts of oligomers is subjected to a catalytic hydrogenation process. The more volatile hydrogenated and partially hydrogenated products are separated by distillation to give the heavier component (MPCA) or bottom product of the original mixture. MPCA is represented by the following chemical structure:

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2이다.Wherein R is independently of each other selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} y = 0-1; z = 0-1; The sum of y and z is 0 to 2.

The present invention relates to a phenalkamine mixture obtained by reacting cardanol (structure according to formula III below) with MPCA (structure according to formula II above) and an aldehyde to obtain a composition represented by the structure according to formula IV below. will be. Formula IV shows a composition of an aldehyde with cardanol and one amino group of MPCA, but it is possible for the other amino groups of MPCA to react in a similar manner to produce a mixture of amine-substituted products.

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; R' = H, C₁-C₁₀ 알킬, Ph, C₅-C₆ 시클로지방족 기, 또는 C₅-C₁₀ 방향족 기이고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2이다. 바람직하게는, R' = H 또는 C₁ 알킬이다.Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. Preferably, R'= H or C ₁ alkyl.

The present disclosure also provides a curing agent composition comprising a phenalkamine mixture of formula (IV).

Preferred curing agent compositions of the present disclosure have an amine hydrogen equivalent weight (AHEW) of about 50 to about 500 based on 100% solids. In another aspect, the present disclosure provides amine-epoxy compositions and cured products made therefrom. For example, an amine-epoxy composition according to the present disclosure comprises a curing agent composition and at least one polyfunctional epoxy resin containing a novel phenalkamine composition comprising at least one cardanol group and having at least two active amine hydrogen atoms. It includes an epoxy composition comprising a.

The present disclosure also provides the use of a curing agent composition comprising a phenalkamine mixture of formula (IV) as a hardener for an epoxy resin.

Articles of manufacture made from the amine-epoxy compositions disclosed herein include, but are not limited to, adhesives, coatings, primers, sealants, curing compounds, building materials, flooring products, and composite products. Additionally, such coatings, primers, sealants, or curing compounds can be applied to metal or cementitious substrates. Mixtures of curing agents and epoxy resins often do not require a "ripening time" to obtain a contact product with high gloss and transparency. The maturation time or growth time is defined as the time between mixing of the epoxy resin and amine and application of the product to the target substrate. It can also be defined as the time required for the mixture to become transparent.

The novel phenalkamine mixture of the present invention can be prepared by reacting cardanol with an aldehyde compound and MPCA to produce a composition represented by the structure according to formula (IV):

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; R' = H, C₁-C₁₀ 알킬, Ph, C₅-C₆ 시클로지방족 기, 또는 C₅-C₁₀ 방향족 기이고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2이다. 바람직하게는, R' = H 또는 C₁ 알킬이다.Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. Preferably, R'= H or C ₁ alkyl.

In a preferred embodiment, the phenalkamine mixture is represented by the structure according to formula (V):

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; R' = H, C₁-C₁₀ 알킬, Ph, C₅-C₆ 시클로지방족 기, 또는 C₅-C₁₀ 방향족 기이고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2이다. 바람직하게는, R' = H 또는 C₁ 알킬이다.Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. Preferably, R'= H or C ₁ alkyl.

In another preferred embodiment, the phenalkamine mixture is represented by the structure according to formula (VI):

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; R' = H, C₁-C₁₀ 알킬, Ph, C₅-C₆ 시클로지방족 기, 또는 C₅-C₁₀ 방향족 기이고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2이다. 바람직하게는, R' = H 또는 C₁ 알킬이다.Where n = 0, 2, 4, or 6;

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. Preferably, R'= H or C ₁ alkyl.

Preferably, the phenalkamine mixture comprises at least one phenalkamine selected from the group:

Where n = 0, 2, 4, or 6; R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group. In a preferred embodiment, the phenalkamine mixture comprises each of the six phenalkamines listed in the group above. Preferably, it comprises a phenalkamine mixture comprising six phenalkamines selected from phenalkamines of formulas (VII), (VIII), (IX), (X), (XI) and (XII). In the curing agent composition, phenalkamine is present in the mixture as follows: 3-9 wt% of phenalkamine of formula (VII), 3-11 wt% of phenalkamine of formula (VIII), 30-45 wt% Phenalkamine of formula (IX), 10-17 wt% of phenalkamine of formula (X), 5-10 wt% of phenalkamine of formula (XI), and 15-30 wt% of phenalka of formula (XII) Min. Preferably, R'= H or C ₁ alkyl.

The present disclosure also provides a curing agent composition comprising a mixture of phenalkamine of any of formula (IV), (V), or (VI). In a preferred embodiment, the curing agent composition comprises a phenalkamine mixture comprising at least one phenalkamine of formula (VII), (VIII), (IX), (X), (XI), or (XII). . In another preferred embodiment, the curing agent composition comprises six phenalkamines selected from phenalkamines of formulas (VII), (VIII), (IX), (X), (XI) and (XII). Contains a mixture of sharpen.

In a preferred embodiment, the curing agent composition may further comprise additional amines having at least two amine functional groups. The phenalkamine curing agent of the present invention can be used in combination with an additional amine curing agent (as a co-curing agent) for curing the epoxy resin.

Preferred examples of further amines having at least two amine functional groups are diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexamethylenediamine ( HMDA), 1,3-pentanediamine (DYTEK ^™ EP), 2-methyl-1,5-pentanediamine ^(Ditec™ A), triaminononane, N-(2-aminoethyl)-1, 3-propanediamine (N ₃ -amine), N,N'-1,2-ethanediylbis-1, 3-propanediamine (N ₄ -amine), or dipropylenetriamine; Arylaliphatic amines such as m-xylylenediamine (mXDA), or p-xylylenediamine; Cycloaliphatic amines such as 1,3-bis(aminomethyl)cyclohexylamine (1,3-BAC), isophorone diamine (IPDA), 4,4'-methylenebiscyclohexanamine, 1,2-diaminocyclo Hexylamine (DCHA), aminopropylcyclohexylamine (APCHA), methylene crosslinked poly(cycloaliphatic-aromatic) amines such as MPCA, aromatic amines such as m-phenylenediamine, diaminodiphenylmethane (DDM), or Diaminodiphenylsulfone (DDS); Heterocyclic amines such as N-aminoethylpiperazine (NAEP), or 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro (5,5)undecane; Polyalkoxyamines or their copolymers, such as 4,7-dioxadecane-1,10-diamine, in which the alkoxy group may be oxyethylene, oxypropylene, oxy-1,2-butylene, oxy-1,4-butylene, 1-propanamine, 3,3'-(oxybis(2,1-ethandiyloxy))bis(diaminopropylated diethylene glycol) (ANCAMINE 1922A), poly(oxy(methyl- 1,2-ethanediyl)), α-(2-aminomethylethyl) ω-(2-aminomethylethoxy) (JEFFAMINE D 230, D-400), triethylene glycoldiamine and oligomer (agent Phamine XTJ-504, Jeffamine XTJ-512), poly(oxy(methyl-1,2-ethandiyl)), α,α'-(oxydi-2,1-ethandiyl)bis(ω-(aminomethyl) Ethoxy)) (Jeffamine XTJ-511), bis(3-aminopropyl)polytetrahydrofuran 350, bis(3-aminopropyl)polytetrahydrofuran 750, poly(oxy(methyl-1,2-ethanediyl) )), α-hydro-ω-(2-aminomethylethoxy) ether and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:I) (Jeffamine T-403), And diaminopropyldiaminopropyl dipropylene glycol.

Other additional amines having at least two amine functional groups include amidoamines and polyamide curing agents. The polyamide curing agent consists of the reaction product of a dimerized fatty acid (dimeric acid) and polyethyleneamine, and typically a certain amount of monomeric fatty acid that helps control the molecular weight and viscosity. A “dimerized” or “dimer” or “polymerized” fatty acid refers to a polymerized acid obtained from an unsaturated fatty acid. Typical monofunctional unsaturated C-6 to C-20 fatty acids also used in the production of polyamides include tall oil fatty acids (TOFA) or soy fatty acids and the like.

Other additional amines having at least two amine functional groups include phenalkamine and phenolic compounds and the Mannich base of amine and formaldehyde. The present disclosure also provides amine-epoxy compositions and cured products made therefrom. The latter is

(a) a curing agent composition comprising the MPCA-derived Mannich base (phenalkamine) of cardanol shown below

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; R' = H, C₁-C₁₀ 알킬, Ph, C₅-C₆ 시클로지방족 기, 또는 C₅-C₁₀ 방향족 기이고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2임)과(Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; the sum of y and z is 0 to 2) and

(b) an epoxy composition comprising at least one polyfunctional epoxy resin

It contains the reaction product of.

The present disclosure also provides the use of a curing agent composition comprising any mixture of phenalkamine of formula (IV), (V) or (VI) as a hardener for epoxy resins. The present disclosure also provides a phenalkamine mixture comprising at least one phenalkamine of formula (VII), (VIII), (IX), (X), (XI), or (XII) as a hardener for epoxy resins. It provides the use of the curing agent composition comprising a. In a preferred embodiment, the curing agent composition is a phenalca comprising at least 6 phenalkamines selected from phenalkamines of formulas (VII), (VIII), (IX), (X), (XI) and (XII). Contains min mixture.

The amine-epoxy composition of the present disclosure includes an epoxy composition comprising a curing agent composition and at least one multifunctional epoxy resin. Multifunctional epoxy resin as used herein refers to a compound containing two or more 1,2-epoxy groups per molecule. The epoxy resin is preferably selected from the group consisting of aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, glycidyl ester resins, thioglycidyl ether resins, N-glycidyl ether resins, and combinations thereof.

Preferred aromatic epoxy resins suitable for use in the present disclosure include glycidyl ethers of polyhydric phenols, including glycidyl ethers of dihydric phenols. Resorcinol, hydroquinone, bis-(4-hydroxy-3,5-difluorophenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4 -Hydroxy-3-methylphenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis-(4-hydroxyphenyl)-propane (commercially Glycidyl ethers such as bisphenol A), bis-(4-hydroxyphenyl)-methane (commercially known as bisphenol F and may contain varying amounts of 2-hydroxyphenyl isomers), Or any combination thereof is more preferred. Additionally, modified divalent phenols of the following structure are also useful in the present disclosure:

Here, R'is a divalent hydrocarbon radical of a divalent phenol, such as the divalent phenols listed above, and p is an average value of 0 to about 7. A substance according to this formula can be prepared by polymerizing a mixture of dihydric phenol and epichlorohydrin or by modifying a mixture of diglycidyl ether of dihydric phenol and dihydric phenol. While the value of p for any given molecule is an integer, the substance is inevitably a mixture that can be characterized by an average value p, which does not necessarily have to be a whole number. Polymeric materials having an average value p from 0 to about 7 can be used in one aspect of the present disclosure.

In one aspect of the present disclosure, the at least one polyfunctional epoxy resin is preferably a diglycidyl ether of bisphenol-A (DGEBA), a modified or higher molecular weight variant of DGEBA, a diglycidyl of bisphenol-F. Dyl ether, diglycidyl ether of novolac resin, or any combination thereof. Higher molecular weight variants or derivatives of DGEBA are prepared by a modification process in which excess DGEBA is reacted with bisphenol-A to produce an epoxy terminated product. The epoxy equivalent weight (EEW) of this product ranges from about 450 to about 3000 or more. Because these products are solid at room temperature, they are often referred to as solid epoxy resins.

In a preferred embodiment, the at least one polyfunctional epoxy resin is a diglycidyl ether of bisphenol-F or bisphenol-A represented by the following structure:

Here, R" = H or CH ₃ and p is an average value of 0 to about 7. DGEBA is represented by the above structure when _{R" = CH 3 and p = 0.} DGEBA or modified DGEBA resins are often used in coating formulations due to their combination of low cost and good performance characteristics. Commercial grade DGEBAs with EEWs in the range of about 174 to about 250, more typically about 185 to about 195 are readily available. At these low molecular weights, the epoxy resin is a liquid and is often referred to as a liquid epoxy resin. One of ordinary skill in the art will appreciate that most grades of liquid epoxy resins are slightly polymeric because pure DGEBA has an EEW of about 174. Also, a resin having an EEW of about 250 to about 450 produced by the modification process is referred to as a semi-solid epoxy resin because it is a mixture of a solid and a liquid at room temperature. Polyfunctional resins having an EEW of about 160 to about 750 on a solid basis are useful in the present disclosure. In another aspect, the multifunctional epoxy resin has an EEW in the range of about 170 to about 250.

Examples of the alicyclic epoxy compound include a polyglycidyl ether of a polyol having at least one alicyclic ring, or a cyclohexene oxide or cyclopentene oxide obtained by epoxidating a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent. Including, but not limited to, a compound comprising. Some specific examples include hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate; 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate; Bis(3,4-epoxycyclohexylmethyl)adipate; Methylene-bis(3,4-epoxycyclohexane); 2,2-bis(3,4-epoxycyclohexyl)propane; Dicyclopentadiene diepoxide; Ethylene-bis(3,4-epoxycyclohexane carboxylate); Dioctyl epoxyhexahydrophthalate; And di-2-ethylhexyl epoxyhexahydrophthalate.

Examples of aliphatic epoxy compounds are polyglycidyl ethers of aliphatic polyols or alkylene-oxide adducts thereof, polyglycidyl esters of aliphatic long chain polyhydric acids, glycidyl acrylates or glycidyl methacrylates are vinyl-polymerized. And copolymers synthesized by vinyl-polymerizing glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. Some specific examples include glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; Triglycidyl ether of glycerin; Triglycidyl ether of trimethylol propane; Tetraglycidyl ether of sorbitol; Hexaglycidyl ether of dipentaerythritol; Diglycidyl ether of polyethylene glycol; And diglycidyl ether of polypropylene glycol; Polyglycidyl ethers of polyether polyols obtained by adding one type or two or more types of alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol, trimethylol propane, and glycerin.

The glycidyl ester resin is obtained by reacting epichlorohydrin with a polycarboxylic acid compound having at least two carboxylic acid groups in the molecule. Examples of such polycarboxylic acids include aliphatic, cycloaliphatic, and aromatic polycarboxylic acids. Examples of aliphatic polycarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, or dimerized or trimerized linoleic acid. Cycloaliphatic polycarboxylic acids include tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid, and aromatic polycarboxylic acids include phthalic acid, isophthalic acid or terephthalic acid.

Thioglycidyl ether resins are derived from dithiols such as ethane-1,2-dithiol or bis(4-mercaptomethylphenyl) ether.

The N-glycidyl resin is obtained by dehydrochlorination of the reaction product of epichlorohydrin and an amine containing at least two amine hydrogen atoms. Such amines are, for example, aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane. However, N-glycidyl resins are also triglycidyl isocyanurate, N,N'-diglycidyl derivatives of cycloalkylene urea, e.g. of ethylene urea or 1,3-propylene urea, and Hydantoin, for example, includes a diglycidyl derivative of 5,5-dimethylhydantoin.

In one or more of the embodiments, the resin component further comprises a reactive diluent. The reactive diluent is a compound that participates in a chemical reaction with the hardener component during the curing process and is incorporated into the cured composition, and is preferably a monofunctional epoxide. Reactive diluents can also be used to change the viscosity and/or curing properties of the curable composition for a variety of applications. For some applications, reactive diluents can impart a lower viscosity to affect flow properties and/or extend pot life and/or improve adhesion properties of the curable composition. For example, reducing the viscosity allows an increase in the level of pigment in the formulation or composition while still allowing easy application or the use of higher molecular weight epoxy resins. Accordingly, it is within the scope of the present disclosure that the epoxy component comprising at least one polyfunctional epoxy resin further comprises a monofunctional epoxide. Examples of monoepoxides include styrene oxide, cyclohexene oxide, and glycidyl ethers such as phenol, cresol, tert-butyl phenol, other alkyl phenols, butanol, 2-ethylhexanol, C4 to C14 alcohols, or combinations thereof Includes, but is not limited to. The polyfunctional epoxy resin can also be present as a solution or emulsion, wherein the diluent is water, an organic solvent or a mixture thereof. The amount of the polyfunctional epoxy resin is about 50% to 100%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, in some cases about 80% of the epoxy component by weight. To about 90%. In one or more of the embodiments, the reactive diluent is less than 60 weight percent of the total weight of the resin component.

Particularly suitable polyfunctional epoxy compounds are diglycidyl ethers of bisphenol-A and bisphenol-F, modified diglycidyl ethers of bisphenol-A and bisphenol-F, and epoxy novolac resins. The epoxy resin may be a single resin, or it may be a mixture of mutually compatible epoxy resins.

The amine-epoxy compositions of the present disclosure preferably have a stoichiometric ratio of epoxy groups in the epoxy composition to amine hydrogens in the curing agent composition, ranging from 1.5:1 to 0.7:1. For example, such amine-epoxy compositions are preferably 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 0.9:1, 0.8:1, or 0.7:1 It can have a stoichiometric ratio. In another aspect, the stoichiometric ratio ranges from 1.3:1 to 0.7:1, or from 1.2:1 to 0.8:1, or from 1.1:1 to 0.9:1.

The MPCA-derived Mannich base (phenalkamine) and amine co-curing agent epoxy composition of the combined cardanol of the present disclosure is preferably in the epoxy composition in the range of 1.5:1 to 0.7:1. It has a stoichiometric ratio of amine hydrogens. For example, such amine-epoxy compositions have stoichiometric ratios of 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 0.9:1, 0.8:1, or 0.7:1. Can have. In another aspect, the stoichiometric ratio ranges from 1.3:1 to 0.7:1, or from 1.2:1 to 0.8:1, or from 1.1:1 to 0.9:1.

Preferably, the weight ratio of the MPCA derived Mannich base (phenalkamine) of cardanol and the amine co-curing agent is from about 1:1 to about 1:0.05. In another embodiment, preferably the weight ratio of the MPCA-derived Mannich base (phenalkamine) of cardanol and the amine co-curing agent is from about 1:0.75 to about 1:0.25.

This disclosure also

(i) cardanol represented by the following formula

(Where n = 0, 2, 4, or 6);

(ii) MPCA represented by the following formula

은 서로 독립적으로 시클로헥실 및 페닐로부터 선택되고; A는 서로 독립적으로 CH₂ 및 NH로부터 선택되고; B는 서로 독립적으로 H, OH, 및 NH₂로부터 선택되고; y = 0-1이고; z = 0-1이고; y와 z의 합은 0 내지 2임); 및(Wherein, R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} y = 0-1; z = 0-1; the sum of y and z is 0 to 2); And

(iii) aldehyde

It relates to a method for preparing a phenalkamine mixture represented by any of the formulas (IV), (V), or (VI), comprising the step of reacting.

In a preferred embodiment of the method, the molar ratio of cardanol to MPCA is in the range of 1:1 to 1:3. In another embodiment, preferably the molar ratio of cardanol to MPCA is in the range of 1:1 to 1:2. Preferably, the molar ratio of MPCA to aldehyde is in the range of 1:1 to 1:3. In another embodiment, preferably the molar ratio of MPCA to aldehyde is in the range of 1:1 to 1:1.2.

In a preferred embodiment of the process, the reaction can be carried out in a one-step process by mixing cardanol with an amine and treating this mixture with formaldehyde at the desired reaction temperature. As an alternative, in another preferred embodiment of the process, cardanol can be mixed, preferably with an aldehyde and treated with MPCA at the reaction temperature. The reaction can be carried out at 40°C-150°C. In another preferred embodiment, the reaction can be carried out at 80°C-120°C. Preferably, the product is obtained by distilling water after the reaction is complete.

In a preferred embodiment of the method, the aldehyde compound used is represented by the formula RCOH, wherein R = H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, C ₅ -C ₁₀ aromatic group or It is a mixture of them. Preferred aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, benzaldehyde, cyclopentanecarboxaldehyde, and cyclohexanecarboxaldehyde. The most preferred aldehydes are formaldehyde and acetaldehyde. Formaldehyde can be used as an aqueous solution or as paraformaldehyde in polymer form.

The molar ratio of cardanol to MPCA and aldehyde determines the degree of reaction of the amino substituents in MPCA. Mixtures of amino substituents are expected. The ratio of the more highly substituted amine substituents on the cardanol (>1) increases when the molar ratio of amino groups to cardanol is >1.0, assuming an equivalent molar ratio of amino groups to aldehydes.

The present disclosure also relates to a method of making a curing agent composition comprising the step of combining a phenalkamine of any formula (IV), (V), or (VI) with an additional amine having at least two amine functional groups.

The compositions of the present disclosure can be used to make a variety of hardened articles of manufacture. Various additives can be used in the formulations and compositions to tailor specific properties, depending on the requirements during the manufacture of the article or for the end-use application. These additives include solvents (including water), accelerators, plasticizers, fillers, fibers such as glass or carbon fibers, pigments, pigment dispersants, rheological modifiers, thixotropes, flow or leveling aids, surfactants. , Antifoam, biocide, or any combination thereof. It is understood that other mixtures or materials known in the art may be included in the composition or formulation and are within the scope of the present disclosure.

The present disclosure also relates to the use of the compositions of the present invention for making hardened articles of manufacture. For example, the article may comprise an amine-epoxy composition including a curing agent composition and an epoxy composition. The curing agent composition may include the MPCA-derived Mannich base of cardanol (phenalkamine). The epoxy composition may include at least one multifunctional epoxy resin. Optionally, depending on the properties desired, various additives may be present in the composition or formulation used to make the article of manufacture. These additives include solvents (including water), accelerators, plasticizers, fillers, fibers such as glass or carbon fibers, pigments, pigment dispersants, rheological modifiers, thixotropes, flow or smoothing aids, surfactants, antifoams, biocides. , Or any combination thereof. The choice and amount of these additives is up to the manufacturer's choice. Representative accelerators that can be used include boron trifluoride amine complexes, substituted phenols such as 2,4,6-tri(dimethylaminomethyl)phenol, tertiary amines such as benzyldimethylamine and imidazole, but not necessarily no.

Preferred articles according to the present disclosure include coatings, adhesives, primers, sealants, curing compounds, building materials, flooring products, composite products, laminates, potting compounds, grouts, fillers, cementitious grouts or self-smoothing flooring. However, it is not limited to this. Coatings based on such amine-epoxy compositions may contain diluents such as water or organic solvents, depending on the needs of the particular application. Coatings can contain various types and levels of pigments when used in paint and primer applications. The amine-epoxy coating composition has a thickness in the range of 40 to 400 μm (micrometer), preferably 80 to 300 μm, more preferably 100 to 250 μm when used in a protective coating applied to a metal substrate. Includes layers. Additionally, the coating composition, when used in a flooring product or building material, comprises a layer having a thickness in the range of 50 to 10,000 μm, depending on the type of product and the required end-characteristics. Coating products that provide limited mechanical and chemical resistance include layers having a thickness in the range of 50 to 500 μm, preferably 100 to 300 μm, while coating products such as, for example, good mechanical and chemical resistance. The self-smooth flooring material that provides a layer comprises a layer having a thickness in the range of 1,000 to 10,000 μm, preferably 1,500 to 5,000 μm.

To prepare the article of manufacture, additional ingredients or additives may be used with the composition of the present disclosure. Additionally, such coatings, primers, sealants, curing compounds or grouts can be applied to metal or cementitious substrates.

The selected relative amount of the epoxy composition relative to the amount of the curing agent composition may vary depending on, for example, the end-use article, its desired properties, and the manufacturing method and conditions used to make the end-use article. For example, in coating applications using certain amine-epoxy compositions, the incorporation of more epoxy resin relative to the amount of the curing agent composition results in increased drying time but improved appearance as measured by increased hardness and glossiness. Coatings with a can result.

As is well known to those skilled in the art, a variety of substrates are suitable for application of the coatings of the present invention provided they are properly surface treated. Such substrates include, but are not limited to, concrete and various types of metals and alloys such as steel and aluminum. The coatings of the present disclosure are suitable for painting or coating large metal objects or cementitious substrates, including ships, bridges, industrial facilities and equipment, and flooring.

The coating of the present invention can be applied by any number of techniques including spray, brush, roller, paint glove, and the like. To apply a very high solids content or 100% solids coating of the present invention, a multi-component spray application equipment can be used, in which the amine and epoxy components are mixed within the spray gun itself in the line leading to the spray gun. Or, as the two components exit the spray gun, the two components are mixed. With this technique, not only the amine reactivity is enhanced, but the pot life of the formulation is typically shortened due to the increased solids content, so that restrictions related to the pot life of the formulation can be relaxed. The use of heated multi-component equipment can improve ease of application by reducing the viscosity of the component.

Construction and flooring applications include compositions comprising an amine-epoxy composition of the present disclosure in combination with concrete or other materials commonly used in the building industry. Applications of the compositions of the present disclosure include primers, deep penetration primers, coatings, curing compounds, and/or their as sealants for old and new concrete, as referred to in ASTM C309-97, which is incorporated herein by reference. Including, but not limited to, uses. As a primer or sealant, the amine-epoxy composition of the present disclosure may be applied to the surface to improve adhesive bonding prior to application of the coating. Regarding concrete and cement applications, coatings are agents used to create protective or decorative layers or coats by being applied to a surface. Crack injection and crack fill products can also be made from the compositions disclosed herein. The amine-epoxy compositions of the present disclosure can be mixed with a cementitious material such as a concrete mixture to form a polymer or modified cement, tile grout, and the like. Non-limiting examples of composite products or articles comprising the amine-epoxy compositions disclosed herein include tennis rackets, skis, bicycle frames, airplane wings, glass fiber reinforced composites, and other molded products.

In certain applications of the curing agent composition of the present disclosure, the coating can be applied to a variety of substrates such as concrete and metal surfaces at low temperatures with a fast cure rate and good coating appearance. This is of particular importance in top-coat applications where good aesthetics are desired, and provides a solution to a longstanding challenge in industries where fast low temperature curing with good coating appearance is still to be achieved. Faster low-temperature curing rates can reduce service or equipment downtime and, for outdoor applications, extend the working season even in cold climates.

Fast epoxy curing agents allow amine-cured epoxy coatings to cure to a high degree of cure within a short period of time. The cure rate of the coating is monitored by the thin film cure time (TFST), which evaluates the coating drying time. The thin film curing time is divided into 4 stages: 1-phase, set to touch; 2-phase, tack free: 3-phase, dry hard; And four-phase, curing dry through. The three-phase drying time suggests how quickly the coating cures and dries. In the case of a fast ambient cure coating, the three-phase drying time is less than 6 hours or less than 4 hours or preferably less than 4 hours. Low temperature curing typically refers to a cure temperature of below ambient temperature, 10°C or 5°C, or in some cases 0°C. In the case of rapid low temperature curing, the three-phase drying time at 5° C. is less than 16 hours, where a significant productivity advantage is provided if the three-phase drying time is less than 10 hours, preferably less than 8 hours.

How well a coating cures is measured by the degree of cure. The degree of cure is often determined using DSC (Differential Scanning Calorimetry) techniques well known to those skilled in the art. A fully cured coating will have a degree of cure of at least 85%, or at least 90%, or at least 95% after 7 days at ambient temperature (25° C.). The fully cured coating will have a degree of cure of at least 80%, or at least 85%, or at least 90% after 7 days at 5°C.

Many of the fast low temperature epoxy curing agents can cure epoxy resins quickly. However, especially at a low temperature of 10°C or 5°C, since the compatibility of the epoxy resin and the curing agent is poor, phase separation occurs between the resin and the curing agent, and the curing agent migrates to the coating surface, resulting in bad, as evidenced by a sticky and cloudy coating. The appearance of the coating results. The good compatibility between the epoxy resin and the curing agent results in a transparent gloss coating with good carbamide resistance and good coating appearance. The curing agent composition of the present disclosure provides a combination of a fast cure rate and good compatibility with a high degree of cure.

Example

These examples are provided to demonstrate certain aspects of the invention and will not limit the scope of the claims appended hereto.

Example 1: Synthesis of phenalkamine of MPCA having a molar ratio of cardanol:MPCA:formaldehyde (1:1:1)

Cardanol (298 g, 1.0 mol) and MPCA (350 g, 1.0 mol) were charged to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel and temperature probe.} The mixture was heated to 80°C. A 37% solution of formaldehyde (81g, 37wt.%, 30g, 1.0 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (34.7 g) and benzyl alcohol (173 g). The resulting product had a viscosity of 5,710 mPa·s at 23° C. and a theoretical AHEW of 150 g/eq.

Example 2: Synthesis of phenalkamine of MPCA having a molar ratio of cardanol:MPCA:formaldehyde (1:1.5:1.0)

Cardanol (298 g, 1.0 mol) and MPCA (525 g, 1.50 mol) were charged to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel and temperature probe.} The mixture was heated to 80°C. A 37% solution of formaldehyde (81g, 37wt.%, 30g, 1.0 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (43.95 g) and benzyl alcohol (219.74 g). The resulting product had a viscosity of 6,290 mPa·s at 23° C. and a theoretical AHEW of 154 g/eq.

Example 3: Synthesis of phenalkamine of MPCA with a molar ratio of cardanol:MPCA:formaldehyde (1:1.5:1.25)

Cardanol (298 g, 1.0 mol) and MPCA (525 g, 1.50 mol) were charged to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel and temperature probe.} The mixture was heated to 80°C. A 37% solution of formaldehyde (101.35g, 37wt.%, 37.5g, 1.25 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (44.10 g) and benzyl alcohol (220.5 g). The resulting product had a viscosity of 10,970 mPa·s at 23° C. and a theoretical AHEW of 182 g/eq.

Example 4: Synthesis of phenalkamine of MPCA having a molar ratio of cardanol:MPCA:aminopropyl cyclohexylamine:formaldehyde (1:0:0.8:0.2:1.0)

Cardanol (298 g, 1.0 mol), MPCA (280 g, 0.8 mol) and aminopropyl cyclohexylamine (31.25 g, 0.2 mol) were added to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel and temperature probe.} Charged. The mixture was heated to 80°C. A 37% solution of formaldehyde (81g, 37wt.%, 30g, 1.0 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (32.7 g) and benzyl alcohol (163.6 g). The resulting product had a viscosity of 2,440 mPa·s at 23° C. and a theoretical AHEW of 233 g/eq.

Example 5: Synthesis of phenalkamine of MPCA with a molar ratio of cardanol:MPCA:aminopropyl cyclohexylamine:formaldehyde (1:0:1.2:0.3:1.0)

Cardanol (298 g, 1.0 mol), MPCA (420 g, 1.2 mol) and aminopropyl cyclohexylamine (46.88 g, 0.3 mol) were added to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel and temperature probe.} Charged. The mixture was heated to 80°C. A 37% solution of formaldehyde (81g, 37wt.%, 30g, 1.0 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (40.9 g) and benzyl alcohol (204.5 g). The resulting product had a viscosity of 2,250 mPa·s at 23° C. and a theoretical AHEW of 230 g/eq.

Example 6: Synthesis of phenalkamine of MPCA having a molar ratio of cardanol:MPCA:triaminonan:formaldehyde (1:0:0.65:0.65:1.3)

Cardanol (298 g, 1.0 mol), MPCA (227.5 g, 0.65 mol) and triaminononane (112.65 g, 0.65 mol) were added to a 3-neck 1 L round bottom flask equipped with an N _{2 inlet, addition funnel, and temperature probe.} Charged. The mixture was heated to 80°C. A 37% solution of formaldehyde (105.4g, 37wt.%, 39g, 1.3 mol) was added to maintain the reaction temperature of 80-90°C. After addition, the mixture was kept at 90-95° C. for 1 h. Water was distilled at 120° C. to give the product as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (34.41 g) and benzyl alcohol (172.03 g). The resulting product had a viscosity of 2,100 mPa·s at 23° C. and a theoretical AHEW of 136 g/eq.

Performance test

Unless otherwise specified, a curing agent mixture was prepared by mixing the components given in the above examples with the epoxy component of a standard bisphenol-A based epoxy resin (Epon 828, DER 331 type) of EEW 190. The formulations used are specified in Table 1. They were then mixed using a stoichiometric level of 1:1 (amine:epoxy equivalent).

<Table 1> Clear coat formulation screening-MPCA phenalcamine

-The EDA-based phenalkamine in form [E] is the commercial product Sunmid® CX105 (former-Evonik). Anchor K54 was added to the formulation to achieve the same accelerator level as present in all MPCA based formulations (Form [A]-[D]).

Form [F] is an example of a blend of Example 1 and the fast co-amine crosslinker Ancamin® 2801 (formerly Evonik).

The formulation as specified in Table 1 was subjected to a series of application tests to determine its performance characteristics. The test protocol revised according to the situation is specified in Table 2.

<Table 2> Test method

Gel time characterizes the time it takes for the composition to convert from liquid to gel. The gel time of the amine-epoxy composition was measured according to ASTM D2471 using a TECHNE gelation timer model FGT 6. Drying time or thin film curing time (TFST) was determined according to ASTM D5895 using a Beck-Koller recorder. An amine-epoxy coating was prepared on standard glass panels with a wet film thickness of 150 μm WFT (wet film thickness) using a Bird applicator to achieve a dry film thickness of ±100 μm. The coating was cured at 23° C. and 5° C. and 60% relative humidity (RH) in a Luner (TPS) environmental chamber. Data for all systems evaluated are reported in Table 3.

<Table 3> Performance characteristics of MPCA phenalkamine curing agent

The coating compositions based on the curing agent of the present invention exhibit several properties that are improved when cured at both 23[deg.] C. and 5[deg.] C. compared to those obtained with commercially available standard EDA based phenalkamine. This includes faster thin film drying time, hardness development and improved low temperature surface appearance, which is most pronounced when the coating is cured under adverse low temperature conditions. This result is considered a significant performance advantage for this type of coating, since faster property development and improved low temperature cure performance can provide productivity benefits in the marine and protective coating coatings market. Form [F] is one example where the addition of a second curing agent to the novel MPCA phenalkamine to form a co-mixture can also improve performance characteristics. In this example, 5% of Ancamine 2801 curing agent lowered the viscosity of the initial curing agent shown in Example 1 by ±40%, and was further cured at low temperature without adversely affecting other properties such as water spot resistance. Improve deployment.

At 23[deg.] C. all coatings showed good gloss development and did not have any greasy amines and surface defects. At lower application temperatures, MPCA-based coatings maintained a very high gloss and grease-free surface, while the reference phenalkamine used in Form [E] exhibited reduced gloss and the clear coating slightly The turbidity developed, which became more pronounced when this system was applied and cured at 5°C. The gloss and surface retention of the MPCA-phenalkamine-based formulations developed in Examples 1, 2 and 6 were better than those of the EDA-based control, which is an improved compatibility with the MPCA amine-based curing agent technique. Implies last name. The results obtained clearly show that the coating containing the curing agent of the present invention possesses both fast curing and good coating appearance, implying good compatibility between the curing agent and the epoxy resin.

Many amine-based systems are susceptible to premature water point tolerance and carbamization. The latter is that free amines present on the coating surface react with atmospheric moisture and carbon dioxide to form an insoluble white salt on the coating surface as a result. To evaluate this, a transparent coating was applied to a clean Lenata chart with a wet film thickness of about 75 μm (wet film thickness) using a bird applicator. The Renata chart was washed with ethanol before use. The coating was cured for 1 and 7 days at 23° C. and 5° C. and 60% relative humidity (RH). A lint-free cotton patch was placed on the test panel so that it was at least 12 mm from the edge of the panel. The cotton patch was moistened with 2-3 ml of demineralized water and then covered with a suitable lid (eg watch glass). The panel was left for the specified time (standard time is 24h). Thereafter, the patch was removed and the coating was dried using a cloth or tissue. Panels were immediately inspected and graded for carbamization. In the tests used by Evonik, Grade 5 corresponds to an excellent surface without carbamization, while Grade 0 corresponds to excessive whitening or severe carbamification. For the water point test, water droplets are applied to the coating in the absence of a lint-free cloth. The water point tolerance rating is the same as in the case of carbamization. The data as summarized in Table 3 suggest that coatings cured using the curing agent of the present invention provide improved carbamization and water point resistance compared to the reference phenalkamine, especially when applied at a low temperature of 5°C.

Chemical resistance study

Several of the amine curing agent based formulations were also evaluated for their basic chemical resistance properties. In this test, a cured puck having a weight of approximately 20.00 g (diameter ±55mm, thickness ±10mm) was prepared. Immersion studies according to ASTM D543 were performed using a standard liquid bisphenol-A based (DGEBA, EEW = 190) epoxy resin cured using the curing agent of Example 1 at 23° C. for 7 days. Two samples were tested for each reagent. Table 4 shows the average percent weight change after immersion in various chemicals for 7 and 28 days at 23°C.

<Table 4>

Chemical resistance of MPCA-phenalkamine-continuous immersion

These studies show that the coating composition based on the MPCA phenalkamine curing agent of the present invention exhibits very good chemical resistance to a variety of chemical reagents. What stands out most over the standard EDA based phenalkamine is its excellent resistance to xylene mixtures and methyl isobutyl ketone (MIBK). In this study, the puck based on Form [A] showed a very low level of weight gain during immersion, while the EDA control showed slight swelling of 18.9% and 44.4%, respectively, 28 days after immersion in MIBK and xylene. It showed an increase in weight.

Claims (16)

A phenalkamine mixture comprising at least one phenalkamine represented by the structure of formula (IV):

Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. The phenalkamine mixture according to claim 1, wherein at least one phenalkamine is represented by the structure of formula (V):

Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. The phenalkamine mixture according to claim 1, wherein at least one phenalkamine is represented by the structure of formula (VI):

Where n = 0, 2, 4, or 6;

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or C ₅ -C ₁₀ aromatic group; y = 0-1; z = 0-1; The sum of y and z is 0 to 2. The method of claim 3, wherein the at least one phenalkamine

Is selected from the group consisting of, wherein n = 0, 2, 4, or 6; R'= H, C ₁ -C ₁₀ alkyl, Ph, C ₅ -C ₆ cycloaliphatic group, or a phenalkamine mixture with a _{C 5} -C _{10 aromatic group.} The phenalkamine mixture according to claim 4 comprising six phenalkamines from those set forth in claim 4. A curing agent composition comprising the phenalkamine mixture according to any one of claims 1 to 5. The curing agent composition according to claim 6, further comprising an additional amine having at least two amine functional groups. Use of the phenalkamine mixture according to any one of claims 1 to 5 or the curing agent composition according to claim 6 or 7 as a hardener for epoxy resins. It is a method for preparing a phenalkamine mixture according to any one of claims 1 to 5,
(i) cardanol represented by the following formula

(Where n = 0, 2, 4, or 6);
(ii) methylene crosslinked poly(cycloaliphatic-aromatic)amine represented by the following formula

(Where n = 0, 2, 4, or 6; R are each independently selected from _{H and CH 3;}

Are each independently selected from cyclohexyl and phenyl; A is independently of each other _{selected from CH 2} and NH; B is independently of each other selected from _{H, OH, and NH 2;} y = 0-1; z = 0-1; the sum of y and z is 0 to 2); And
(iii) aldehyde
A method comprising the step of reacting. The molar ratio of claim 9, wherein the molar ratio of cardanol to methylene bridged poly(cycloaliphatic-aromatic) amine is in the range of 1:1 to 1:3, and the molar ratio of methylene bridged poly(cycloaliphatic-aromatic) amine to aldehyde Is in the range of 1:1 to 1:3. The method according to claim 9, wherein the cardanol and at least one methylene crosslinked poly(cycloaliphatic-aromatic)amine are mixed at a temperature of 40 to 150° C. and then treated with an aldehyde at a temperature of 40 to 150° C. The method according to claim 9, wherein the cardanol and aldehyde are mixed at a temperature of 40 to 150° C. and then treated with at least one methylene cross-linked poly(cycloaliphatic-aromatic) amine at a temperature of 40 to 150° C. The method of claim 9, wherein the aldehyde is formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, benzaldehyde, cyclopentanecarboxaldehyde And cyclohexanecarboxaldehyde. A method of preparing the curing agent composition of claim 7 comprising combining a phenalkamine mixture of formula (IV) with an additional amine having at least two amine functional groups. Use of a curing agent composition according to claim 6 or 7 or a phenalkamine mixture according to any one of claims 1 to 5 in combination with at least one epoxy resin for the production of hardened articles of manufacture. . The use of claim 15, wherein the article is a coating, adhesive, building material, flooring product, or composite product.